Process for treating coals, tars, mineral oils, and the like, by hydro-genation under high pressure and at high temperature



Jan.` 3, 1933.

S. LFFLER PROCESS FOR TREATING GOALS, TABS, MINERAL OILS, AND THEv LIKE BY HYDROGENATION UNDER HIGH PRESSURE AND AT HIGH Filed Aug. 15, 1930 TEMPERATURE 2 Sheets-Sheet 1 Ruff/M- le mura [Manuf/WWW:

Jan. 3, 1933. s, I FFLER 1,893,423 PROCESS FOR TREATING GOALS, TARS, MINERAL OILSl AND THE LIKE BY HYDROGENATION UNDER HIGH PRESSURE AND AT HIGH TEMPERATURE Filed Aug. 15, 1930 2 Sheets-Sheet 2 Patented Jari. 3, 1933 UNITED STATESA PATENT orrlce STEPHAN LFFLER, DECEASED, LATE BERLIN-CHARLOTTENBURG', GERMANY, BY JENNY ELFRIEDE LFFLER, SOLE HEIR, OF BERLIN-CHARLOTTENBURG, GERT/[AN Y PROCESS FOR TREATING GOALS, TABS, 'MINERAL OIL'S,-AND LIKE, BY HYDRO- GENATION UNDER HIGH PRESSURE AND AT 'HIGH 'TEMPERATURE Application led August 15, 1930,'Sera1 No.

rIhis invention relates to an improvement in the destructive hydrogenation of Adistillable carhonaceous materials, such .as coals of all varieties and hydrocarbons vsuch as tars or oils under high pressure and at high temperature.

Briefiy stated, the invention consists `in employing, before, during and after the reaction, high-pressure steam (superheated or saturated or condensed) forheatingand cooling the participants in the reaction, such as coal, tar, oil, hydrogen, additions and the like. The term participants .in the reaction where herein employed isra'lso intended toinclude the reaction products. The pressure-of said steam should be at least .equal to .that .prevailing in the reaction chamber, or dier :only slightly therefrom, for which purpose the reaction vessel is, for example, connected Adiy rectly or indirectly with the heating and cooling chambers, a control member being interposed if desired.

j Preferably the steam 1s led in closed circuits, the heating or cooling action being controlled in a simple manner fby varying vthe volume in circulation, the-temperature, or the like. The circulation may be positivelyV maintained by means of pumps or the like. For the purpose of Vheat equalization inthe several heating and cooling circulations, a com-mon heat accumulator may be included, the heat content of which is modified, and into which surplus hot steam is admitted. The water level therein must be checked and regui lated.

' As a heat carrier in the pressure-hydrogenation of coal etc., steam oifers a series of important and practical advantages over the gaseous media at present mainly employed `for that purpose.

The apparatus needed for the gaseous heat carriers employed (namely, the plant tor4 generating the respective gases, the high-duty compressor for compressing the gases to 475,643, and in Germany November 27, 1926.

direct heating of the gaseousheat carriers, in

coiled pipes lor the'like, would be dangerous. On the other hand, the interposition of the intermediate heat carrier introduces the drawback of rendering the controlof the tem'- perature tardy.

. The steam lemployed as heat carrier in accordance with this invention, is generated in a high-pressure boiler which., at the same time, supplies the ksteam required for power purposes in thehydrogenation and attendant y plants, and'iseasily and reliably controlled. The outpu-t required is less than when gaseous heat carriers are employed, the gas-producer plant and .highduty compressor for rcompressing the gas, being eliminated. Further, the maintenance of a definite temperature, with only very slight luc-tuationsfand the regulation `of .the temperature, or the alteration in the level of the temperature, is easily and reliably assured,in consequence of the direct heating of the steam in the superheater. Still further, the employment of steam results vmore complete heat utilization of the heat carrier and reaction components, through the .heat exchange between the two,

the preheating of the feed water, the intermediate superheating and the like, and enables a satisfactory equalization of heat and temperature to be obtained in the various heating or cooling circulations, for example by the vinterpostion of a joint heat accumulator, and 'by a storage of heat per se.' A

When steam is employed, the diskv of corrosion is less than in the case of the usually employedheat carrier,hydrogen. Operating 'with ysteam is also far less dangerous than operating with hot hydrogen. Y

Various embodiments of plants for the treatment "of coal and -oill and the like .are 100 illustrated, diagrammatically and by way of example, on the accompanying drawings.

1n Fig. 1 reference 1 denotes the reaction vessel, into which coal or oil or the like is admitted, togetherwith the requisite additions, `at a, the hydrogen for hydrogenation being admitted at b', and the hydrocarbonsV .beingled away at c after the reaction has been completed.y In' many cases the reaction proceeds under heavy pressures (20-100 latmospheres and over) and high temperatures (300-500" The reaction vessel 1 is tenclosed in a pressure casing 2. High-pressure steam forv heating, or for maintaining the reaction temperature, is admitted into the jacket `space at cl, said steam 4being supplied from a directly or indirectly heated boiler 3,'with superheater 4, and distributed into the various pipes at f, by means of suitable control devices. e

rIhe steam issues from the jacket space at e and passes into a heat exchanger 5, in which the hydrogen required for the reaction is heated. The condensate from the hot steam is then returned to the boiler 3, for example by means of a pump P1.

The raw materials, additions, etc., are preheated by steam in a second heat exchanger 6, and the resulting condensate is also returned to the boiler 3 by means of the pump The boiler 3 also supplies steam to an engine 7, the condensate `from which is likewise returned to the boiler 8.

The feed water for the boiler.3,.for example the condensate from theengine plant 7, is forced by a pump P2 into a heat exchanger 8, where it absorbs,.in counterow, the heat of the reaction gases, and is then conveyed to the boiler 3. The improved or treated oil and residues are drawn off from the heat exchanger 8 at g. u

Fig. 2 represents another embodiment, with positive steam circulation in the several heating and cooling systems, thesame reference characters being employed as in Fig. 1. The steam is generatedin a highpressure boiler 3 by superheated steam introduced from f, is led from the boiler at L, and is forced, in a positive manner by a pump P3 or the like,.thr0ugh the fire-heated superheater 4 and into the consumption pipes at Y A portion of the steam flows through the jacket space of the reaction vessel 1 and then into the heat exchanger 5 for heating the hydrogen. A second portion of the steam serves for preheating the raw materials, additions etc., in the heat'exchanger 6. The steam condensate from 5 andv 6 is ledfback into the boiler 3. A further portionof the steam serves for performing work in the engine plant 7. As in Fig. y 1, the feed-water is preheated, by the reaction gases, yin-the heat exchanger 8, from which the gases are drawn off at g through a throttle 9.

The heating and cooling action can be regulated by varying the delivery of the pump P3, or by modifying the steam temperature, etc. Modification of lthe steam temperature can be eected by the heating of the superheater 4, or by mixing the steam with saturated steam in the various circulations, for example, from i "out, through the pipes 10 and 11', by way of the control devices 12 and 18 Fig. l3- represents a plant in which a joint heat accumulator 14, with water space and steam space, is connected up with the several heating and cooling circulations. In this case, the production and superheating of the steam for the various circulations are effected, for example, in separate, Vheated coils 15, 16 and 17, into which water is forced, at 7c, from the heat accumulator, by means of pumps P4, P5 vand P6. Surplus steam is returned to the heat accumulator by way of pipes 18, 19 and 20. Similarly, the feed water serving to coolthe reaction products, and the condensate from the circulation of the reaction vessel and the preheating of the raw, materials in 1, are led into the heat accumulator'. The water level in said accumulator ischecked by means of a water gauge 21, and is regulated by varying the rate of feed by the pump P2, or by drawing off water at la, by means of a throttle 22. The pressure in the heating and cooling systems is adjusted by the pressure in the reaction chamber, through the agency of a special control device 23, which is connected with the reaction chamberl and the steam space of the heat accumulator 14, by pipes 24 and 25. In this case, the heat exchangers 6 and 8 are designed as double pipe coils.

i What is claimed is 1. A lprocess vfor the destructive hydrogenation of a distillable carbonaceous material, which comprises introducing a hydrogenating gas under a pressure of at least 20 atmospheres and a carbonaceous material into a reaction zone, heating water in a confined space thereby producing high pressure steam, passing the steam through a Zone of still higher temperature, passing part of the steam thus heated into a Zone surrounding the reaction zone and being in indirect heat exchange relationship therewith, thence passing said steam into indirect heat exchange relationship with the incoming hydrogenatingv gas, and thencefreturning the steam to the aforesaid confined space, passing another p art of said steam into indirect heat exchange relationship with the incoming carbonaceous material andthence back to the said confined space, causing a further part of said high pressure steam to do mechanical work, passing the condensate thus produced into indirect heat exchange relationship With the -terial,

reaction products and then returning it to said conlined space.

2. A process for the destructive hydrogenation of a distillable carbonaceous inawhich comprises introducing a hydrogenating gas under a pressure of at least 20 atmospheres and a carbonaceous material into a reaction Zone, heating water in a conlined space thereby producing high pressure steam, pumping the steam to a point of distribution, while simultaneously by means of the pumping regulating the amount of steam and its rate of iiow, passing part of the steam through a zone of still higher temperature, bubbling part of the steam thus heated into the water contained in the said conlined space, passing steam from the point of distribution together with steam coming from the said zone of higher temperature into indirect heat exchange relationship with the reaction zone, thence passing said steam into indirect heat exchange relationship with the incoming hydrogenating gas and thence returning the steam to the aforesaid conned space, passing another part of the steam from the point of distribution together with another part of the steam from the said zone of higher temperature into indirect heat exchange relationship with the incoming carbonaceous material and thence returning it to the confined space, passing water into heat exchange relationship with the reaction products, and then passing it into the said conend space.

3. A process for the destructive hydrogenation of a distillable carbonaceous material, which comprises introducing a hydrogenating gas under a pressure of at least 20 atmospheres and a carbonaceous material into a reaction zone, heating water in a confined space thereby producing high pressure steam, passing the steam through a zone of still higher temperature, passing part of the steam thus heated into a zone surrounding the reaction zone and being in indirect heat exchange relationship therewith, thence passing said steam into indirect heat exchange relationship with the incoming hydrogenating gas, and thence returning the steam to the aforesaid confined space, passing another part of said steam into indirect heat exchange relationship with the incoming carbonaceous material and thence back to the said conned space and bringing the products of the reaction into indirect heat exchange relation with cooling water.

4. A process for the destructive hydrogenation of a distillable carbonaceous material, which comprises introducing a hydrogenating gas under a pressure of atleast 20 atmospheres and a carbonaceous material into a reaction zone, withdrawing reaction products from the reaction zone, heating water in a confined space thereby producing high pressure steam, passing the steam through a zone of still higher temperature,

ship vwith the reaction Zone, thence causing said steam to acquire aV temperature exchange relationship therewith, thence passing said steam into indirect heat exchange relationship with the incoming hydrogenating gas, and thence returning the steam to the aforesaid confined space, passing anotherv aart of said steam into indirectheat exchan e i relationship-,with the incoming carbonaceous material and thence back to the said confined space, causing a further part of said high pressure steam to do mechanical work, passing the condensate Lthus produced into. in` direct ,heat exchange relationship with the reaction products and then returningvit to said ,conned space. Y .y

5. Al process yfor the destructive hydrogenation oi a distillablecarbonaceous material',which comprises Vintroducing a hy.- drogenating, gas under ak pressure of at least 20 atmospheres anda carbonaceous material into a reaction zone, heating water in a confined space thereby producing high pressure steam, pumping the steam to a point of distribution, while simultaneously regulating the amount ofsteam and its rate of flow, passing part of the steam through a zone or" still Vhigher temperature, thereby causing .said steam to-acquire a temperature of not lessv than 300- Celsius, bubbling part of thegsteam thus heated into the. water contained in the said confined space, passing steam from the point of distribution together with steam coming from-the said zone of higher temperature into indirect heat exchange :relation- V passing' said steam into indirect heat exchange relationship-with the incoming Vhydrogenating gas and thence returning the Vsteam to the aforesaid confined space, passing another part ofthe steam from the point ofdistribution together with another part of the steam `from the said zone of higher temperature into indirect heat exchange relationship with the incoming carbonaceous material and thence returning it to the confined space, passing water into heat exchange relationship with the reaction products, and then passing it into the said confined space.

6. A process for the destructive hydrogenation of a distillable carbonaceous material, which comprises introducing a hydrogenating gas under a pressure of at least 20 atmospheres and a carbonaceous material into avreaction zone, heating water in a confined space thereby producing high pressure steam, passing the steam through a zone of a still higher temperature, passing the steam thus heated into a zone surrounding the reaction zone and being in indirect heat exchange relationship therewith, maintaining the steam in said surrounding zone at substantially the pressure of said reaction zone,

thence passing said steam into indirect heat exchange relationship with the incoming hydrogenating gas, and passing another part of said steam into indirect heat exchange relationship with the incoming carbonaceous material.

7. A process for the destructive hydrogenation of a Vdistillable carbonaceous material, which comprises introducing a hydrogenating gas under a pressure of at least 2O atmospheres and a carbonaceous materialY into a reaction zone, heating Water in a confined space thereby producing high pressure steam, passing the steam through a zone of a still higher temperature, passing the steam thus heated into a zone surrounding the reaction zone and being in indirect heat exchange relationship therewith, maintaining the steam in said surrounding Zone at substantially the pressure of said reaction zone, thence passing said steam into indirect heat exchange relationship with the incoming hydrogenating gas, and passing another part of said steam into indirect heat exchange relationship With the incoming carbonaceous material and thence back` to said confined space.

8. In the destructive hydrogenation of a distillable carbonaceous material, treating the said material With a hydrogenating gas under a pressure of at least 2O atmospheres, maintaining a zone containing a participant in the reaction in indirect heat lationship with a steam zone containing high pressure steam having a temperature approximating that Which it is desired to give to said participant in the reaction, by having the one zone surrounding the other and maintaining the pressures in said zones substantially equal by varying the supply of steam to said steam zone in accordance With the pressure in said other Zone.

In testimony whereof I 'affix my signature.

JENNY ELFRIEDE LOFFLER, Sole H6711' of Stephaw Ller, Deceased.

exchange re- 

